Anthracene compound and process of making same.



IINITEU STATES PATEN ll OFFICE.

oscAR BALLY, or MANNHEIM, AND HUGO WOLFF, or LUDWIGSHAFEN- VON-THE-RHINE, GERMANY, ASSIGNORS TO BADISCHE ANILIN 8: SODA FABRIK, OFLUDWVIGSHAFEN-ON-THERHINE, GERMANY, A CORPORA- TION.

Specification of Letters Patent.

Patented Jan. 9, 1906.

Application filed October 10, 1905. Serial No. 282,184.

To all whom it may concern:

Be it known that we, OSCAR BALLY, doctor of philosophy and chemist, acitizen of the Swiss Republic, residing at Mannheim, in the Grand Duchyof Baden, and HUGO WVOLFF, doctor of philosophy and chemist, a subjectof the Grand Duke of Baden, residing at Ludwigshafen-on-the-Rhine, inthe Kingdom of Bavaria, German Empire, have invented new and usefulImprovements in Anthracene Compounds and Processes of Making the Same,of which the following is a specification.

In the specification of Letters Patent N 0. 786,085 is described theproduction of new compounds of the anthracene series by condensingtogether glycerin, or an equivalent thereof, and abeta-amidoanthraquinon body, these new compounds containing a specialgroup to which the name benzanthrone group has been given.

The present invention consists in the production of analogous compoundsfrom alphaamidoanthraquinon bodies, as hereinafter defined, and theobtainment of coloring-matters therefrom.

Maj ert, in the specification of German Patent No. 26,197, describes thecondensation of glycerin with various amidoanthraquinons and states thathe thus obtains anthraquinon quinolins. The only alpha-amidoanthraquinonknown at the date of this German patent were the 1.5 and 1.8dianiidoanthraquinons obtained by nitrating anthraquinon with nitricacid in the presence of sulfuric acid and then reducing the dinitrocompounds so obtained, and we have repeated Maj erts experiments andhave found that these two diamidoanthraquinons on being condensed withglycerin do yield an.

thraquinon quinolins, but do not yield any benzanthrone compound. IVehave discovered that all the other amidoanthraquinons containing ananiido group in the alpha position which are known at the present time,with the exception of alpha-amido-alizarin, on being condensed withglycerin or an equivalent thereofsuch, for instance, as its anhydridsand esters-yield benzanthrone compounds. These new compounds are of usein the preparation of coloring-matters, for (similarly to those obtainedfrom the betaamidoanthraquinons) on being melted with caustic alkalithey yield violet-blue coloringmatters. The amidoanthraquinons which canbe used for the purposes of our invention includealpha-amidoanthraquinon, 1.4-diamidoanthraquinon and 1.2 amidohydroxyanthraquinon, and, of course, in any case their homologues,sulfoacids, and halogen derivatives may be employed.

The new compounds obtained according to our invention contain abenzanthrone grouping and consist, when dry, of brown powders, which aresoluble in concentrated sulfuric acid, yielding yellow to brownsolutions with green fluorescence.

The following examples will serve to further illustrate the nature ofour invention and the way in which it can be carried into racticaleffect; but our invention is not conned to these examples. The parts areby weight.

Example 1: Dissolve twenty (20) parts of alpha-amidoanthraquinon inthree hundred (300) parts of sulfuric acid, (containing eightytwo (82)per cent. of H SOQ add eighteen (18) parts of glycerin and heat the massfor about half an hour (thirty minutes) at a temperature of fromonehundred and fifty (150) to one hundred and fifty-five (155) degreescentigrade. Allow the mixture to cool, then pour it onto ice, and filteroff the condensation product, which separates out in yellowish-brownflakes. When dry, it is a yellowish-brown powder which is insoluble inwater, but which is partly soluble in dilute acids, and from suchsolutions it can be precipitated by the addition of alkali. Its solutionin concentrated sulfuric acid is yellowish-brown and has a strong greenfluorescence. It yields reddish yellow solutions in alcohol, benzene,and xylene, and it can be purified by recrystallization from alcohol andobtained in golden-yellow leaflets. Thus purified the compound iscompletely soluble in dilute acids and has a melting-point of twohundred and fifty-seven (257) degrees centigrade. It dissolves inconcentrated sulfuric acid, yielding a golden-yellow solution with astrong green fluorescence.

Example 2: Dissolve ten (10) parts of 1.4- diamidoanthraquinone in twohundred (200) parts of sulfuric acid (containing ninetyamid has beenacted upon.

eight (98) per cent. of H 80 and add, slowly, forty parts of ice. Addtwelve (12) parts of glycerin and heat the mixture for about forty-fiveminutes to a temperature of one hundred and fifty (150) degreescentigrade. When the mixture is cold, pour it into water and filter offthe condensation product, which separates out in brown flakes, whichwhen dry constitute a brown powder which is'insoluble in water, but ispartly soluble in dilute acids, and it can be precipitated from suchsolutions by the addition of alkali. It is soluble in concentratedsulfuric acid, yielding a yellowish-brown solution with a greenfluorescence.

Example 3: Dissolve ten (10) parts of 1.2- amido-hydroxy anthraquinon(alpha aliza- -rinarnid) in two hundred and fifty (250) parts. ofsulfuric acid (containing about eighty-two (82) per cent. of H and addten (10) parts of glycerin. Heat the mixture at a temperature of onehundred and fifty (150) degrees centigrade until all the alizarin Pourthe melt into a large excess of water and filter. The condensationproduct is a brown powder, which can be'crystallized from dilutealcohol, and thus be obtained as small brown needles -which can bedissolved in concentrated sulfuric acid, yielding a yellow solution witha slight green fluorescence. The said needles are also soluble incaustic-soda solution,

yielding a violet-red solution with a dark green fluorescence. I

Now what we claim is 1. The process for the production of anthracenecompounds by condensing a hereinbefore defined alpha amidoanthraquinonbody with glycerin.

2. The process for the production of anthracene compounds by condensinga hereinbefore defined alpha amidoanthraquinon body with glycerin in thepresence of sulfuric acid.

3. The process for the production of anthracene compound by condensingalphaamidoanthraquinon with glycerin in the presence of sulfuric acid.

4. As new articles of manufacture the anthracene compounds obtainable bycondensing a hereinbefore-defined alpha-amidoanthraquinon body withglycerin, which compounds contain a benzanthrone grouping and which,when dry, consist of brown powders which are soluble in concentratedsulfuric acid yielding yellow to brown solutions with green fluorescenceand which on melting with caustic alkali yield violet-bluecoloring-matters.

5. As a new article of manufacture the anthracene compound obtainable bycondensing alpha amidoanthraquinon with glycerin, which compoundcontains a benzanthrone grouping and which, when dry, consists of abrown powder which is soluble in concentrated sulfuric acid yielding ayellowish-brown solution with a green fluorescence and which on meltingwith caustic alkali yields a violet-blue coloring-matter.

In testimony whereof we have hereunto set our hands in the presence oftwo subscribing witnesses.

OSCAR BALLY. HUGO WVOLFF.

Witnesses:

ERNEST F. EHRHARDT, J. Auto. LLOYD.

